Sensitive and Selective Electrochemical Analysis of Methyl‐parathion (MPT) and 4‐Nitrophenol (PNP) by a New Type p‐NiTSPc/p‐PPD Coated Carbon Fiber Microelectrode (CFME)

A novel modified carbon fiber microelectrode (CFME) was obtained by combination of tetrasulfonated nickel phtalocyanine (p‐NiTSPc) electroformed film associated to para‐phenylenediamine (p‐PPD) electropolymerized outer‐coating. The modified CFMEs where denoted C/p‐NiTSPc and C/p‐NiTSPc/p‐PPD, respectively. These electrodes are dedicated to the organophosphates compounds (OPs) methyl‐parathion (MPT) and para‐nitrophenol (PNP). Our contribution shows that both OPs can be determined simultaneously on the unmodified and modified C/p‐NiTSPc CFMEs. A clear electrocatalytic activity towards both MPT and PNP redox process was observed, for the first time, in presence of p‐NiTSPc. The obtained sensitivity for the C/p‐NiTSPc CFME was 80 nA L mg^?1 in the concentration range 0.01 to 10 mg/L with a detection limit of 40 μg/L. Also the combination of p‐NiTSPc and p‐PPD electrodeposited films show, for the first time, the possibility to discriminate on the C/p‐NiTSPc/p‐PPD CFME between MPT and PNP. Stability experiments were also conducted for 3 weeks in acetate buffer showing a good reproductibility of the sensitivity to PNP vs. time in presence of MPT with a little loss of sensitivity (5%) after 3 weeks.     

Preparation of Organophilic Nanohybrid Kaolinite and Application to the Electrochemical Detection of Organic Pesticide

Novel organophilic nanohybrid materials (K‐TDD) were obtained by the grafting of 1,2‐tetradecanediol (TDD) onto the surface of kaolinite (K). XRD, IR, TGA‐DTG, and SEM characterization showed that TDD grafting results in a partial exfoliation of kaolinite layers. This material was used to modify a glassy carbon electrode (GCE/K‐TDD) and applied for the trace analysis of methyl parathion (MP). The signal of MP recorded on GCE/K‐TDD was more intense compared to the unmodified GCE or to one modified with a film of natural kaolinite. Several parameters that can affect the stripping response were systematically investigated to optimize the sensitivity of the organokaolinite‐modified electrode. A linear calibration curve for MP was obtained in the concentration range from 2×10⁻⁶ to 14×10⁻⁶ mol .L⁻¹ in acetate buffer (pH 6), giving a detection limit of 9×10⁻⁸ mol .L⁻¹. The sensitivity of the method was found to be 2.42 μA/μM for the range of concentrations that gives a linear calibration curve. The electrode was shown to be very stable, with the electrochemical response of MP decreasing by only 1.5 % after a series of nine measurements. The interference of various inorganic ions and organic compounds likely to influence the stripping determination of the MP were also examined. The results showed that the GCE/K‐TDD electrode was effective in solutions containing interfering species and could be applied for the quantification of MP pesticide in natural water.     

Identification of Metabolites of Methylparathion in Plant,Water and Soil

ABSTRACT

A GC-MS study was carried out to identify the decay products of methyl parathion in water, soil and rooted vegetable (radish) at different time intervals. The water (pH 5.5 and 8.0), soil (pH 7.5) and radish samples collected after the first half life shows the presence of O,O dimethyl O-p-nitro-2 or 3-hydroxyphenyl phosphoorothioate which persists upto the 30th day in the alkaline water and soil samples. However, in acidic water methyl parathion is oxidized to give methylparaoxon.

Radish samples show the presence of two other products. These are identified as O,O-dimethyl o-p-aminophenyl -phosphoorothioate and O,O-dimethylo-p-hydroxyphenyl phosphoorothioate. The study indicates that the half life of methyl parathion in different media is nearly the same but its metabolites are not identical.     

Electrochemical analysis of methylparathion pesticide by a gemini surfactant-intercalated clay-modified electrode

In this study, an hybrid material obtained by the intercalation of a gemini surfactant between the layers of smectite-type clay, was fully characterized by X-ray diffraction (XRD), infrared spectroscopy (FTIR) and N₂ adsorption-desorption experiments (BET method). To ascertain the intercalation process of the starting clay by the dimeric surfactant, the permselectivity and ion exchange properties of the organoclay were investigated by ion exchange voltammetry using [Fe(CN)₆]³⁻ and [Ru(NH₃)₆]³⁺ as redox probes, by the means of a clay film-modified electrode. Due to its organophilic character, the surfactant-intercalated complex was evaluated as electrode modifier for the accumulation of methylparathion (MP) pesticide. The electroanalytical procedure involves two steps: preconcentration under open-circuit followed by voltammetric detection by square wave voltammetry: the peak current obtained (after 5 min preconcentration in 4 × 10⁻⁵ mol L⁻¹ MP) on a glassy carbon electrode coated by a thin film of the modified clay was more than five times higher than that exhibited by the same substrate covered by a film of the pristine clay. This opens the way to the development of a sensitive method for the detection of the pesticide. Many parameters that can affect the stripping response (surfactant loading of the hybrid material, film composition, pH of the detection medium, preconcentration time, electrolysis potential and duration as well as some other instrumental parameters) were systematically investigated to optimize the sensitivity of the organoclay-modified electrode. After optimization, a linear calibration curve for MP was obtained in the concentration range from 4 × 10⁻⁷ to 8.5 × 10⁻⁶ mol L⁻¹ in acetate buffer (pH 5), with a detection limit of 7 × 10⁻⁸ mol L⁻¹ (signal-to-noise ratio equal to 3). The interference effect of various inorganic ions likely to influence the stripping determination of the pesticide was also examined, and the described method was applied to spring water analysis.